Chromium-based fluorination catalyst, production method thereof, and fluorination method

Abstract: To produce hydrofluorocarbons with high productivity, and to provide a catalyst for that purpose and a production method of the catalyst, there is provided a chromium-based fluorination catalyst comprising Cr, Ga, O and F as the essential constituent elements, prepared by firing starting materials containing gallium element and chromium element at a temperature of from 300 to 500°C in an inert gas atmosphere to form a catalyst precursor, and partially fluorinating said catalyst precursor by bringing said catalyst precursor into contact with hydrogen fluoride or with fluorine-containing halogenated hydrocarbon at a temperature of from 300 to 500°C.

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improved method for producing a fluorination catalyst which is useful for producing with high productivity hydrofluorcarbons which do not contain chlorine and are hence free from destruction of the ozone layer (hereinafter referred to as "HFC"), among others, difluoromethane (hereinafter referred to as "HFC-32"), 1,1,1,2-tetrafluoroethane (hereinafter referred to as "HFC-134a") and pentafluoroethane (hereinafter referred to as "HFC-125"). 2. Description of the Related Art A typical example of the industrial production methods of the HFCs is the method which replaces halogens other than F by F by bringing a hydrogen-containing halogenated hydrocarbon into contact with HF (in many cases, addition of HF using an unsaturated halogenated hydrocarbon as the starting material and the exchange reaction of the halogens other than F with F are simultaneously conducted). However, the reaction does not smoothly proceed in most cases, and the production quantity of the HFCs greatly depends on the catalyst used. An example of the most difficult reaction is the synthesizing reaction of HFC-134a by fluorination of 1-chloro-2,2,2-trifluoroethane (hereinafter referred to as "HCFC-133a"), and this reaction is obviously an endothermic reaction which is not advantageous thermodynamically. Therefore, the reaction is generally carried out at a relatively high temperature by allowing HF in an amount exceeding a stoichiometric amount to be co-present with HCFC-133a. According to Japanese Unexamined Patent Publication (Kokai) No. 55-27138, for example, HFC-134a is obtained at a yield of 32% by conducting the reaction at a temperature of 400°C using a compound obtained by treating CrF 3 ·3H 2 O with air, as the catalyst. The reaction at such a high reaction temperature promotes coking of the catalyst and reduces catalyst life. To prevent coking, an attempt was made to allow oxygen to be co-present inside the reaction gas (Japanese Unexamined Patent Publication (Kokai) No. 55-27139), but this method is not desirable because chlorinated by-products increase. To restrict the formation of the chlorinated by-products, Japanese Examined Patent Publication (Kokoku) No. 5-88690 discloses a method which conducts the reaction in the presence of oxygen by using the catalyst which is obtained by fluorinating a non-Cr-based CoCℓ 2 /Aℓ 2 O 3 , but this catalyst has low activity and low productivity. For these reasons, attempts have been made to prolong service life of the catalysts. Thus, Japanese Unexamined Patent Publication (Kokai) No. 2-172933 clarifies that a catalyst comprising a halide or oxide containing at least one kind of elements selected from the group consisting of Aℓ, Mg, Ca, Ba, Sr, Fe, Ni, Co and Mn, and containing also Cr, has high durability (long life). EP 502605 discloses a Cr-based catalyst supporting Zn. Further, Japanese Unexamined Patent Publication (Kokai) No. 4-34694 discloses a catalyst comprising Cr 2 O 3 which is partially fluorinated and supports Ru and Pt, and Japanese Unexamined Patent Publication (Kokai) No. 5-269382 discloses a catalyst consisting of chromium oxide and nickel oxide as principal components thereof, as a catalyst having long service life. However, coking on the catalyst is vigorous in the fluorination reaction of hydrogen-containing halogenated hydrocarbon in the production of HFCs, and even the catalysts described above do not have a sufficient service life. In other words, it has been necessary in the past to select the reaction conditions under which coking difficultly occurs. Because the progress of coking is greater when the ratio of the HF feed quantity to the feed quantity of organic materials (hereinafter called the "molar ratio") is smaller, the progress of coking is retarded by increasing this molar ratio when the conventional fluorination catalyst is used. However, the increase of the molar ratio means a decrease of the feed quantity of the organic materials (when SV is kept constant), and means a drop of STY (space time yield). It can be therefore concluded that the catalyst life is prolonged according to the prior art at the sacrifice of STY to a certain extent. Accordingly, if a catalyst which suffers less from coking than the conventional catalysts and which has longer service like could be obtained, it would become possible not only to prolong catalyst life but also to carry out the reaction at a lower molar ratio, so that the improvement of productivity can be expected. In the light of the background described above, the present invention aims at providing a fluorination catalyst having long service life in the production of the HFCs, which may be used in the method of efficiently producing HFCs by bringing a halogenated hydrocarbon having 1 to 4 carbon atoms into contact with HF in a gaseous phase. SUMMARY OF THE INVENTION The inventors of the present invention have earnestly carried out studies to solve the problems described above, and have already found out that a catalyst obtained by heating or firing a starting material comprising chromium hydroxide as the main component at a temperature of 350°C to 500°C in the presence of hydrogen has a high catalyst activity allowing the fluorination reaction at a low temperature and has a long catalyst service life. This method is disclosed in EP-A-0 641 598, a copending European application. Another method for producing a fluorination catalyst comprising indium, chromium, oxygen and fluorine as essential constituent elements comprises the treatment of a catalyst precursor, comprising indium and chromium, by contacting it with hydrogen fluoride or a fluorine containing halogenated hydrocarbon at a temperature of 300 to 500°C (EP-A-0 629 440, a co-pending European application. By further investigations of the present inventors it was found that a catalyst which is obtained by first heating a starting material comprising Ga and Cr in an inert gas atmosphere at a temperature of 300°C to 500°C and then partially fluorinating the thus obtained catalyst precursor by contacting the catalyst precursor with hydrogen fluoride or fluorine-containing halogenated hydrocarbon at a temperature of 300°C to 500°C, has a catalyst service life equal to or longer than that of the above-mentioned catalysts on the basis of this finding the present invention was reached. Thus, the present invention resides in a method for preparing a fluorination catalyst containing gallium and chromium which comprises firing or heating a starting material containing gallium element and chromium element at a temperature of 300 to 500°C in an inert gas atmosphere to form a catalyst precursor, and partially fluorinating said catalyst precursor by bringing said catalyst precursor into contact with hydrogen fluoride or with a fluorine-containing halogenated hydrocarbon at a temperature of 300 to 500°C. DESCRIPTION OF PREFERRED EMBODIMENTS Although it is not much preferred that the chromium-based fluorination catalyst according to the present invention contains large quantities (in the wt% order) of alkali metals as constituent elements other than Ga, Cr, O and F, the catalyst may contain other elements in the % order. Particularly, at least one kind of elements selected from the Groups 8, 9, 10, 11 and 12 (New IUPAC naming Method), among others, Co, Ni, Cu, Zn, Cd, etc., which are expected to provide an activity promotion effect as a promoter or a co-catalyst, may be contained within the range of 0.001 to 0.5 and preferably 0.003 to 0.2, in terms of the atomic ratio to Cr. The catalyst according to the present invention can be prepared by using a compound containing Ga and Cr (e.g. an oxide and a hydroxide) as a catalyst precursor, fluorinating this catalyst precursor by HF, F 2 or a halogenated hydrocarbon containing fluorine in the molecules thereof, and so replacing partially O and OH by fluorine. The compounds containing Ga and Cr can be supported on a support, and examples of suitable supports include activated carbon, alumina, aluminum fluoride, magnesium fluoride, and so forth. Any of known methods such as a kneading method, an impregnation method, a coprecipitation method, etc., can be employed in the method of preparing the catalyst precursor, and any materials can be used for the starting materials for preparing the catalyst precursor so long as they are available on the industrial scale. Among the methods described above, the impregnation method and the coprecipitation method are preferred because they can introduce Ga in Cr in a high dispersion degree. Among others, coprecipitation is further preferred because this method can arbitrarily control the dispersion state of Ga. Accordingly, an example of the preferred method of preparing the catalyst precursor comprises the steps of allowing a solution in which salts of Ga and Cr are dissolved to react with a precipitating agent to form a precipitate, and conducting filtration, washing, drying and firing of the precipitate (example of the coprecipitation method), or the steps of impregnating chromium oxide or chromium hydroxide with a solution of the Ga compound, and conducting drying and firing (example of the impregnation method). When a support is used, the catalyst precursor can be prepared by impregnating the support with the solution of the Ga and Cr compounds, and conducting drying and firing. Examples of further preferred methods of preparing the catalyst precursor include the method which comprises adding in advance a precipitating agent (an alkali) to a slurry of chromium hydroxide (particularly trivalent hydroxide) in an amount sufficient to neutralize at least the Ga and Cr salts to be later added, then adding slowly a mixed solution of the Ga and Cr salts, and conducting separation, washing, drying and firing of the resulting product, and the method which comprises dropping either simultaneously or alternately a solution of the Ga and Cr salts and a precipitating agent so as to form a slurry while controlling the pH of the reaction solution in the range of from 6 to 12 and particularly preferably, 6.5 to 10, and then conducting filtration, washing, drying and firing of the reaction product. Nitrates, chlorides and sulfates can be suitably used as the Ga and Cr compounds as the starting materials for the preparation of the catalyst precursor. Among them, the nitrates and the chlorides are particularly preferred for the coprecipitation method and the impregnation method, respectively. Preferred examples of precipitating agents are ammonia, sodium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium hydroxide, potassium carbonate, potassium hydrogencarbonate, ammonium carbonate and ammonium hydrogencarbonate. Particularly preferred among them is ammonia. When a molded shape is desired as the shape of the catalyst, tablet-molding is carried out before, or after, firing described above, or extrusion molding is carried out before drying. Drying is preferably carried out at a temperature within the range of 80 to 130°C, particularly 90 to 120°C, in an atmosphere of air or an inert gas such as N 2 , for at least 30 minutes, but other drying methods such as vacuum drying can also be used. Firing is preferably carried out at a temperature within the range of 300 to 600°C, preferably 350 to 500°C, particularly 360 to 400°C. The firing atmosphere may be a reducing gas atmosphere, but the Ga and Cr-containing catalyst of the present invention, if fired in an inert gas atmosphere, can have a catalyst service life equivalent to that of a catalyst fired in a H 2 -containing atmosphere. Even firing in a H 2 -containing atmosphere usually requires purging with an inert gas to purge O 2 present in the system prior to the firing or to purge H 2 after the firing and prior to introduction of air into the system. Firing in an inert gas atmosphere allows that such purging following the firing is eliminated and the process simplified. Firing in an inert gas atmosphere reduces the catalyst production cost since it does not use a flammable gas and a special equipment for venting such gas is not required. Thus, it is advantageous from the economical viewpoint to use an inert gas atmosphere for firing. The inert gas atmosphere used here means an atmosphere in which substantially no chemically active gases such as O 2 and H 2 are contained and the inert gas comprises 99.9% by volume or more. The inert gas includes N 2 , He, Ne, Ar, Kr, etc., with N 2 being preferred due to its cheapness. Thus, a preferred method of firing comprises substituting the inside of a firing chamber by N 2 and, in a N 2 flow raising the temperature to 360 to 400°C and keeping the temperature for at least one hour, preferably 2 to 10 hours. The temperature is then lowered to 150°C, preferably to 120°C and air is gradually introduced into the system to an O 2 concentration close to 20% by volume. The fired catalyst precursor is then removed. The adequate flow rate of N 2 is 10 to 10000 h -1 as GHSV (converted to the standard state) and the pressure is conveniently atmospheric pressure to 10 kg/cm 2 G. The preparation of the catalyst precursor may be conducted by any of the methods described above or by any of the heretofore known methods, but the atomic ratio of Ga to Cr (hereinafter called "Ga/Cr ratio") must be kept within the range of 0.0001 to 0.15, preferably 0.001 to 0.1 and particularly preferably 0.003 to 0.05. If the Ga/Cr ratio is smaller than the range described above, the effect of preventing coking cannot be obtained and if the Ga/Cr ratio is too great, the reaction rate drops undesirably. The Ga/Cr ratio can be easily controlled by regulating the proportion of powders to be mixed in the case of the kneading method and by controlling the concentrations of the Ga and/or Cr compound solutions and the composition of the solutions in the case of the impregnation method and the coprecipitation method. The fluorination catalyst according to the present invention further requires O and F as the essential constituent elements. Though the suitable ranges of the O and F contents change in accordance with the Ga/Cr ratio and with the preparation method of the catalyst precursor, at least 0.3 wt%, on the basis of the total weight of the catalyst, is necessary for each of the components. A preferred range of the O content is from 1 to 25 wt%, and a preferred F content is from 15 to 45 wt%. In order to allow the catalyst to contain O and F, the compound containing Ga and Cr is fluorinated by a gas of HF, F 2 or a halogenated hydrocarbon containing F in the molecule thereof, as already described. Among them, the fluorination method using HF is excellent from the aspect of the cost. The fluorination temperature of the catalyst precursor before the reaction is from 300 to 500°C and particularly preferably, from 300 to 450°C. The concentration of the fluorinating agent such as HF may be from 0.1 to 100 vol%, but the fluorinating agent is preferably diluted by an inert gas such as N 2 , whenever necessary, so that the temperature rise (hereinafter called "ΔT") due to exothermy is at most 50°C. A suitable gas flow rate is 10 to 10,000 h -1 by GHSV, and the pressure ranges from the atmospheric pressure to 20 kg/cm 2 G. A preferred example of the fluorination method of the catalyst precursor supplies HF and N 2 at atmospheric pressure and at 300 to 400°C so that the HF concentration becomes 5 to 30 vol%, and then starts fluorination. After a hot spot passes through the precursor packing layer, the HF concentration and the pressure are raised to at least 90 vol% and 2 to 10 kg/cm 2 G, respectively, while caution is paid to exothermy, and the treatment is continued under the final condition until at least exothermy no longer exists. Firing of the catalyst precursor and its fluorination described above can be carried out inside the same reactor so long as it is made of Inconel or Hastelloy, and the operation can conveniently proceed. The fluorination catalyst which contains Ga, Cr, O and F as the essential constituent elements and can be produced in the manner described above can be applied to the fluorination of halogenated hydrocarbons by HF, and is particularly effective for the fluorination reaction of H-containing halogenated hydrocarbons. In other words, coking more difficultly proceeds than in the conventional fluorination catalysts such as chromium oxyfluoride, and a longer catalyst life can be accomplished. The term "H-containing halogenated hydrocarbons" used in the present invention represents those halogenated hydrocarbons which contain H mainly in C 1 to C 4 molecules, and concrete examples include CHCℓ 3 , CH 2 Cℓ 2 , CH 2 FCℓ, CH 3 Cℓ, C 2 HCℓ 3 , C 2 H 2 Cℓ 2 , C 2 H 3 Cℓ, C 2 HCℓ 3 , C 2 HFCℓ 4 , C 2 HF 2 Cℓ 3 , C 2 HF 3 Cℓ 2 , C 2 HF 4 Cℓ, C 2 H 2 Cℓ 4 , C 2 H 2 FCℓ 3 , C 2 H 2 F 2 Cℓ 2 , C 2 H 2 F 3 Cℓ, C 2 H 3 Cℓ 3 , C 2 H 3 FCℓ 2 , C 2 H 3 F 2 Cℓ, C 2 H 4 Cℓ 2 , C 2 H 4 FCℓ, C 2 H 5 Cℓ, C 3 H 2 F 4 Cℓ 2 , and C 3 HF 4 Cℓ 3 . Further, Cℓ of the hydrocarbons described above may be replaced either completely or partially by Br. Among others, the fluorination catalyst of the present invention is effective for the fluorination reaction of CH 2 Cℓ 2 , CH 2 FCℓ (HCFC-31), CHCℓ=CCℓ 2 (trichloroethylene), CF 3 CH 2 Cℓ (HCFC-133a), CCℓ 2 =CCℓ 2 (perchloroethylene), CF 3 CHCℓ 2 (HCFC-123), CF 3 CHFCℓ (HCFC-124), etc., which are believed as a synthesis route for the production of CH 2 F 2 (HFC-32), CH 2 FCF 3 (HFC-134a) and CF 3 CHF 2 (HFC-125) which have drawn an increasing attention in recent years as the HFCs which are free from possible destruction of the ozone layer. The fluorination may be carried out by a reaction method such as a fixed bed, a fluidized bed, a moving bed method, etc., but generally, the molar ratio of HF to the halogenated hydrocarbon is 0.5 to 20, the temperature is from 200 to 400°C, the pressure is from the atmospheric pressure to 20 kg/cm 2 G, and SV is from 50 to 100,000 h -1 . Since coking does not easily proceed in the fluorination catalyst of the present invention, the molar ratio of HF to the halogenated hydrocarbons can be made smaller than in the case where the conventional fluorination catalysts are used. Accordingly, not only catalyst life can be improved, but high STY can also be improved and hence, productivity can be improved. EXAMPLES Hereinafter, the present invention will be concretely explained with reference to Examples and Comparative Examples, but the invention is not naturally limited to such an explanation. By the way, the Ga/Cr ratio represents the atomic ratio of each element contained in the catalyst determined by chemical analysis, and the molar ratio in the reaction example represents the molar ratio of HF to the halogenated hydrocarbons. SV is a value converted to the standard condition, and the pressure is a gauge pressure. (Catalyst Preparation Example 1) A Ga and Cr-containing aqueous solution was obtained by dissolving 0.92g of Ga(NO 3 ) 3 ·nH 2 O (Ga content: 18.9 wt%) and 10g of Cr(NO 3 ) 3 ·9H 2 O in 240g of pure water. Next, aqueous ammonia (NH 3 ) was further added to a slurry of chromium hydroxide prepared by mixing an aqueous Cr(NO 3 ) 3 solution with aqueous ammonia. After pH of the slurry (Cr content in the slurry = 1.4 wt%) was adjusted to 9 in this way, the Ga and Cr-containing aqueous solution described above was added dropwise to 840g of this slurry in the course of about 20 minutes so as to prepare the slurry of hydroxide containing Ga and Cr. The resulting slurry was filtrated, was sufficiently washed with pure water and was dried at 110°C for 12 hours. The resulting solid was pulverized, was mixed with graphite and was thereafter pelletized by a tableting machine. The pellet was packed into a firing tube and was fired at 400°C for 4 hours in the N 2 stream to obtain a catalyst precursor. The resulting precursor was packed into a reaction tube made of Inconel and was subjected to the fluorination treatment first in a 20 vol% HF stream diluted by N 2 at 350°C and the atmospheric pressure, then in a 100 vol% HF stream while the supply of N 2 was cut off, and further in a 100 vol% HF stream while the pressure was raised to 5 kg/cm 2 G. The composition of the pellet after this treatment is tabulated below: Ga: 0.76, Cr: 56.9, O: 17.5, F: 22.1 The result of analysis represents that the Ga/Cr ratio was 0.01. (Catalyst Preparation Example 2) A slurry of chromium hydroxide prepared by mixing an aqueous Cr(NO 3 ) 3 solution and aqueous ammonia (NH 3 ) with sufficient stirring was filtrated, and was sufficiently washed by pure water and was then dried at 110°C for 12 hours. The resulting solid was pulverized, and an aqueous GaCℓ 3 solution (prepared by dissolving 0.43g of GaCℓ 3 in 25g of pure water) was slowly dropped to 50g of the pulverizate so obtained. The powder thus wetted was again dried at 110°C for 12 hours, was then mixed with graphite and was thereafter pelletized by a pelletizing machine. Thereafter, the fluorination treatment was carried out in the same way as in Preparation Example 1. The composition of the pellet after this treatment is tabulated below. Ga: 0.38, Cr: 57.4, O: 17.0, F: 23.5 The result of analysis represents that the Ga/Cr ratio was 0.005. (Catalyst Preparation Example 3) A solution prepared by dissolving 75g of Cr(NO 3 ) 3 ·9H 2 O and 0.69g of Ga(NO 3 ) 3 ·nH 2 O in 200 mℓ of pure water and 50 mℓ of 28 wt% aqueous ammonia were charged dropwise into a 1ℓ container storing therein 100 mℓ of pure water in the course of about 20 minutes while the flow rates of two kinds of aqueous solutions were controlled so that the pH of the reaction solution was within the range of 7.5 to 8.5. The resulting slurry was filtrated, was sufficiently washed by pure water and was thereafter dried at 110°C for 12 hours. The catalyst was prepared by thereafter following the procedures of Preparation Example 1. The Ga/Cr ratio determined from the result of analysis was 0.01. (Catalyst Preparation Example 4) After 110g of CrCℓ 3 ·6H 2 O and 0.58g of GaCℓ 3 were dissolved in 78g of pure water, 100g of activated alumina was immersed in the solution so as to absorb the full amount of the solution. The alumina was then dried at 120°C for 12 hours and was packed into a firing tube made of glass. Firing was carried out first at 350°C for 3 hours in air stream and then at 400°C for 4 hours in the H 2 stream. The resulting precursor was packed into a reaction tube made of Inconel, and the fluorination treatment was carried out first at 350°C and the atmospheric pressure in a 20 vol% HF stream diluted by N 2 , then in a 100 vol% HF stream while the feed of N 2 was cut off, and further in a 100 vol% HF stream while the pressure was raised to 3 kg/cm 2 G. The Ga/Cr ratio determined from the result of analysis was 0.008. (Catalyst Preparation Example 5) The catalyst was prepared by following the procedures of Preparation Example 1 except that an aqueous solution containing Ga, Cr and Zn prepared by additionally adding 2.23g of Zn(NO 3 ) 2 ·6H 2 O to the Ga- and Cr-containing aqueous solution used in Preparation Example 1 was used. The Ga/Cr ratio determined from the result of analysis was 0.01, and the Zn/Cr ratio was 0.03. (Comparative Catalyst Preparation Example 1) A catalyst precursor was prepared by following the procedures of Catalyst Preparation Example 1 except that the pellet prepared in Catalyst Preparation Example 1 was fired in a H 2 flow at 400°C and the fluorination treatment was then carried out in the same way as in Catalyst Preparation Example 1. The composition of the pellet after this treatment is tabulated below. Ga: 0.79, Cr: 58.6, O: 19.1, F: 19.5 The result of analysis represents that the Ga/Cr ratio was 0.01. (Comparative Catalyst Preparation Example 2) A catalyst precursor not containing Ga was prepared by following the procedures of Catalyst Preparation Example 1 except that Ga(NO 3 ) 3 ·nH 2 O was not added to the aqueous solution to be added dropwise to the slurry of chromium hydroxide. The resulting catalyst precursor was subjected to the fluorination treatment in the same way as in Preparation Example 1. The composition of the pellet after this treatment is tabulated below. Cr: 58.9, O: 18.5, F: 20.6 (Comparative Catalyst Preparation Example 3) A catalyst precursor having a large addition amount of Ga was prepared by following the procedures of Preparation Example 1 except that 18.4g of Ga(NO 3 ) 3 ·nH 2 O was added to the aqueous solution to be added dropwise to the slurry of chromium hydroxide, and the resulting catalyst precursor was subjected to the fluorination treatment in the same way as in Catalyst Preparation Example 1. The composition of the pellet after this treatment is tabulated below. Ga: 12.2, Cr: 45.5, O: 16.3, F: 22.7 The result of analysis represents that the Ga/Cr ratio was 0.2. (Reaction Example 1) The catalyst prepared in Catalyst Preparation Example 1 was pulverized and classified, and 2.5 mℓ of granules between 0.71 mm and 1 mm were packed into a reaction tube made of Inconel. Then, the fluorination reaction of HCFC-133a was carried out under the following activity evaluation condition and HFC-134a yield was measured. Thereafter, the reaction condition was changed to the following condition in which degradation was likely to occur (hereinafter called the "accelerated degradation condition"), and the reaction product was left standing for 15 hours. However, the HFC-134a yield remained at a constant value of about 11%. Thereafter, the reaction condition was again returned to the activity evaluation condition described above, and the degree of the drop of activity was measured. Table 1 illustrates the HFC-134a yields before and after accelerated degradation and a yield ratio before and after accelerated degradation. Activity evaluation condition: temperature: 320°C, pressure: atmospheric pressure, HF/HCFC-133a molar ratio: 8, SV: 1,500 h -1 Accelerated degradation condition: temperature: 360°C, pressure: atmospheric pressure, HF/HCFC-133a molar ratio: 1, SV: 2,000 h -1 (Reaction Examples 2 - 5) The degree of drop of activity due to accelerated degradation was measured in accordance with Reaction Example 1 except that the catalysts prepared in Catalyst Preparation Examples 2 - 5 were used. The results are tabulated in Table 1. (Comparative Reaction Examples 1 - 2) The degree of the drop of activity due to accelerated degradation was measured in accordance with Reaction Example 1 except that the catalysts prepared in Comparative Catalyst Preparation Examples 1 - 2 were used. The result is tabulated in Table 1. Yield comparison of HFC-134a before and after accelerated degradation catalyst yield before acc-deg. (%) yield after acc-deg. (%) yield ratio Prep. Example 1 23.6 16.8 0.71 Prep. Example 2 20.5 15.8 0.77 Prep. Example 3 22.9 18.1 0.79 Prep. Example 4 16.1 10.5 0.65 Prep. Example 5 23.9 16.7 0.70 Comp. Prep. Ex. 1 24.1 16.9 0.70 Comp. Prep. Ex. 2 23.8 10.3 0.43 Comp. Prep. Ex. 3 12.4 9.2 0.74 In the table above, the yield represents the yield of HFC-134a and the yield ratio represents the ratio of the yields before and after accelerated degradation. It could be understood from the result described above that in the case of the catalyst containing Ga in an atomic ratio of Ga/Cr of 0.01, even fired in N 2 atmosphere, the catalyst has a catalyst service life longer than that of the catalyst not containing Ga and fired in H 2 atmosphere and has catalyst performance equivalent to the catalyst containing Ga added thereto and fired in H 2 atmosphere, particularly the yield after accelerated degradation is almost the same between the two catalysts. Accordingly, it could be understood that in accordance with the present invention, a catalyst having a long service life can be produced at a relatively cheap cost. It could also understood from Comparison Reaction Example 2 that if the amount of addition of Ga was too great, activity of the catalyst undesirably dropped. (Reaction Example 6) The fluorination reaction of HCFC-123 was carried out under the following condition using the catalyst prepared in Catalyst Preparation Example 1 in accordance with Reaction Example 1, and the degree of the drop of activity was measured. Activity evaluation condition: temperature: 320°C, pressure: atmospheric pressure, HF/HCFC-133a molar ratio: 4, SV: 1,000 h -1 Accelerated degradation condition: temperature: 370°C, pressure: atmospheric pressure, HF/HCFC-133a molar ratio: 1, SV: 1,000 h -1 The yield ratio of HFC-125 before and after accelerated degradation was 0.45. As described above, since the fluorination catalyst according to the present invention has long service life and can be prepared at a relatively low cost, hydrofluorocarbons can be produced with high productivity.

Claims: A method for preparing a fluorination catalyst containing gallium and chromium which comprises firing starting materials containing gallium element and chromium element at a temperature of from 300 to 500°C in an inert gas atmosphere to form a catalyst precursor, and partially fluorinating said catalyst precursor by bringing said catalyst precursor into contact with hydrogen fluoride or with a fluorine-containing halogenated hydrocarbon at a temperature of from 300 to 500°C. A method according to claim 1, wherein an atomic ratio of gallium to chromium is from 0.0001 to 0.15. A method according to claim 1, wherein an atomic ratio of gallium to chromium is from 0.001 to 0.1. A method according to claim 1, wherein an atomic ratio of gallium to chromium is from 0.003 to 0.05. A method according to any of the claims 1 through 4, which results in a catalyst comprising gallium, chromium,oxygen and fluorine and further containing at least one element selected from the group consisting of cobalt, nickel, zinc and cadmium. A method according to any of claims 1 through 5, which is comprises the coprecipitation of starting materials containing gallium element and chromium element. A method according to any of claims 1 through 5, which comprises the impregnation of starting materials containing gallium element and chromium element. A method according to any of the claims 1 to 7 wherein the starting material containing the gallium element is a nitrate, a chloride or a sulfate of gallium.

Inventors: NAKAJO TETSUO, TSUJI KATSUYUKI, NAKAJO, TETSUO, TSUJI, KATSUYUKI, NAKAJO, TETSUO, C/O SHOWA DENKO K.K., TSUJI, KATSUYUKI, C/O SHOWA DENKO K.K.
Applicants: SHOWA DENKO KK, SHOWA DENKO KABUSHIKI KAISHA
Application year: 1994
Main classification: B01J27
IPC codes: B01J23, B01J27